Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Multiple-Filled Skutterudites

Filled skutterudites are prospective intermediate temperature materials for␣thermoelectric power generation. CoSb₃-based n-type filled skutterudites have good electrical transport properties with power factor values over 40 μW/cm K² at elevated temperatures. Filling multiple fillers into the crystallographic voids of skutterudites would help scatter a broad range of lattice phonons, thus resulting in lower lattice thermal conductivity values. We report the thermoelectric properties of n-type multiple-filled skutterudites between 5 K and 800 K. The combination of different fillers inside the voids of the skutterudite structure shows enhanced phonon scattering, and consequently a strong suppression of the lattice thermal conductivity. Very good power factor values are achieved in multiple-filled skutterudite compared with single-element-filled materials. The dimensionless thermoelectric figure of merit for n-type filled skutterudites is improved through multiple-filling in a wide temperature range.     

Thermoelectric Properties of Ca-Filled CoSb<Subscript>3</Subscript>-Based Skutterudites Synthesized by Mechanical Alloying

Ca _z Co_4−x (Fe/Mn) _x Sb₁₂ skutterudites were prepared by mechanical alloying and hot pressing. The phases of mechanically alloyed powders were identified as γ-CoSb₂ and Sb, but they were transformed to δ-CoSb₃ by annealing at 873 K for 100 h. All specimens had a positive Hall coefficient and Seebeck coefficient, indicating p-type conduction by holes as majority carriers. For the binary CoSb₃, the electrical conductivity behaved like a nondegenerate semiconductor, but Ca-filled and Fe/Mn-doped CoSb₃ showed a temperature dependence of a degenerate semiconductor. While the Seebeck coefficient of intrinsic CoSb₃ increased with temperature and reached a maximum at 623 K, the Seebeck coefficient increased with increasing temperature for the Ca-filled and Fe/Mn-doped specimens. Relatively low thermal conductivity was obtained because fine particles prepared by mechanical alloying lead to phonon scattering. The thermal conductivity was reduced by Ca filling and Fe/Mn doping. The electronic thermal conductivity was increased by Fe/Mn doping, but the lattice thermal conductivity was decreased by Ca filling. Reasonable thermoelectric figure-of-merit values were obtained for Ca-filled Co-rich p-type skutterudites.     

Electrical Transport Properties of Filled CoSb<Subscript>3</Subscript> Skutterudites: A Theoretical Study

We present an investigation of electronic structures and electrical transport properties of some filled CoSb₃ skutterudites by combining ab initio projected augmented plane-wave calculations and Boltzmann transport theory with electron group velocity evaluated by the momentum matrix method. The systems are studied in a 2 × 2 × 2 supercell of Co₄Sb₁₂ to reveal the effects induced by different filler atoms and their filling fractions. The temperature dependences of the Seebeck coefficient and power factor are studied, and they are in good agreement with experimental data. Our results reveal an optimal filling fraction for n-type filled CoSb₃ skutterudites and related compounds for achieving the highest power factor values.     

Electrodeposition and Thermoelectric Characteristics of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> and Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Films for Thermopile Sensor Applications

A thermopile sensor was processed on a glass substrate by electrodeposition of n-type bismuth telluride (Bi-Te) and p-type antimony telluride (Sb-Te) films. The n-type Bi-Te film electrodeposited at −50 mV in a 50 mM electrolyte with a Bi/(Bi + Te) mole ratio of 0.5 exhibited a Seebeck coefficient of −51.6 μV/K and a power factor of 7.1 × 10⁻⁴ W/K² · m. The p-type Sb-Te film electroplated at 20 mV in a 70 mM solution with an Sb/(Sb + Te) mole ratio of 0.9 exhibited a Seebeck coefficient of 52.1 μV/K and a power factor of 1.7 × 10⁻⁴ W/K² · m. A thermopile sensor composed of 196 pairs of the p-type Sb-Te and the n-type Bi-Te thin-film legs exhibited sensitivity of 7.3 mV/K.     

Microstructure and Thermoelectric Properties of Yb-Filled Skutterudites Prepared by Rapid Solidification

Single-phase nanostructured bulk Yb_0.2Co₄Sb₁₂ skutterudites have been prepared by combining a melt spinning technique with spark plasma sintering. The effects of a pre-annealing process on the microstructure and phase composition of ribbon samples and bulk materials are investigated. After the pre-annealing process, average grain size increases from 200 nm to 300 nm for ribbon samples and from 250 nm to 350 nm for bulk materials, and nearly single-phase skutterudites have formed. Because of the nanostructure, the thermal conductivity of bulk skutterudites notably decreases 25% at 800 K. As␣a result, the ZT values are improved compared with starting material prepared by the traditional method.     

Structure and Thermoelectric Properties of Te- and Ge-Doped Skutterudites CoSb<Subscript>2.875−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>0.125</Subscript>Te<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

n-Type CoSb_2.875−x Ge_0.125Te _x (x = 0.125 to 0.275) compounds with different Te contents have been synthesized by a melt–quench–anneal–spark plasma sintering method, and the effects of Te content on the structure and thermoelectric properties have been investigated. The results show that all specimens exhibited n-type conduction characteristics. The solubility limit of Te in CoSb_2.875−x Ge_0.125Te _x is found to be x = 0.25. The solubility of Te in CoSb₃ is increased through charge compensation of the element Ge. The room-temperature carrier concentration N _p of CoSb_2.875−x Ge_0.125Te _x skutterudites increases with increasing Te content, and the compounds possess high power factors. The maximum power factor of 3.89 × 10⁻³ W m⁻¹ K⁻² was obtained at 720 K for the CoSb_2.625Ge_0.125Te_0.25 compound. The thermal conductivity decreases dramatically with increasing Te content due to strong point defect scattering. The maximum value of the thermoelectric figure of merit ZT = 1.03 was obtained at 800 K for CoSb_2.625Ge_0.125Te_0.25, benefiting from a lower thermal conductivity and a higher power factor. The figure of merit is competitive with values reported for single-filled skutterudites.     

Synthesis and Thermoelectric Properties of InzCo4?xFexSb12 Skutterudites

The thermoelectric properties of In-filled and Fe-doped CoSb₃ (In _z Co_4−x - Fe _x Sb₁₂) skutterudites prepared by encapsulated induction melting were examined. A single δ-phase was obtained successfully by subsequent annealing at 823 K for 120 h. The Hall and Seebeck coefficients of the In _z Co_4−x Fe _x Sb₁₂ samples had positive signs, indicating p-type conduction. The electrical conductivity was increased by Fe doping, and the thermal conductivity was decreased by In filling due to phonon scattering. The thermoelectric properties were improved by In filling and Fe doping, and were closely related to the optimum carrier concentration and phonon scattering.     

Low Thermal Conductivity and Enhanced Thermoelectric Performance in In and Lu Double-Filled CoSb<Subscript>3</Subscript> Skutterudites

The thermoelectric properties of indium (In) and lutetium (Lu) double-filled skutterudites In _x Lu _y Co₄Sb₁₂ prepared by high-pressure synthesis were investigated in detail from 4 K to 365 K. Our results indicate that In and Lu double filling can remarkably reduce the thermal conductivity, and substantially improve the thermoelectric performance. A thermoelectric figure of merit of ZT = 0.27 for In_0.13Lu_0.05Co_4.02Sb₁₂ was achieved at 365 K, being larger by one order of magnitude than that for CoSb₃. It is thought that the large difference in resonance frequencies of the In and Lu elements broadens the range of normal phonon scattering in the multifilled skutterudites, helping to achieve an even lower lattice thermal conductivity. This investigation suggests that an effective way to improve the thermoelectric performance of skutterudite materials is to use In and Lu double filling.     

Thermoelectric Properties of Triple-Filled BaxYbyInzCo4Sb12 Skutterudites

Indium-filled skutterudites are promising power generation thermoelectric materials due to the presence of an InSb nanostructure that lowers the thermal conductivity. In this work, we have investigated thermoelectric properties of triple-filled Ba _x Yb _y In _z Co₄Sb₁₂ (0 ≤ x, y, z ≤ 0.14 actual) compounds by measuring their Seebeck coefficient, electrical conductivity, thermal conductivity, and Hall coefficient. All samples were prepared by a melting–annealing–spark plasma sintering method, and their structure was characterized by x-ray diffraction and transmission electron microscopy (TEM). TEM results show the development of an InSb nanostructure with a grain size of 30 nm to 500 nm. The nanostructure is present in all samples containing In and is also detected by specific heat measurements. The Seebeck and Hall coefficients indicate that the compounds are n-type semiconductors. Electrical conductivity increases with increasing Ba content. Thermal conductivity is strongly suppressed upon the presence of In in the skutterudite structure, likely due to enhanced boundary scattering of phonons on the nanometer-scale InSb inclusions. The highest thermoelectric figure of merit is achieved with Ba_0.09Yb_0.07In_0.06Co₄Sb_11.97, reaching ZT = 1.25 at 800 K.     

Large Closed-Circuit Seebeck Current in Quaternary (Ti,Zr)NiSn Heusler Alloys

In the (Ti _x ,Zr _y )Ni _w Sn _z quaternary system with a composition near (x + y):w:z = 1:1:1 the existence of the half-Heusler (HH) phase has been confirmed, where Ti and Zr occupy one of the three lattice positions substitutionally. The goal of this study is to characterize the thermoelectric (TE) properties of such materials. TE properties were measured at large temperature differences up to ΔT = 800 K, exhibiting Seebeck voltages of about ±50 mV corresponding to Seebeck coefficients above 0.07 mV/K, with the highest value measured for the (Ti_0.4Zr_0.6)Ni_0.9Sn_1.1 composition. Fe and Mn doping could not improve these values further. Measurements under closed-circuit conditions showed very high currents of 0.4 mA for specimens at this particular composition. According to the composition, interfaces between full-Heusler and HH phases are responsible for an electron pull-out phenomenon due to the electric field at their interfaces. First-principle calculations of the electronic band structure confirm this explanation for why (TiZr)NiSn and CrNiSn are p-type TEs whereas NbNiSn is an n-type TE. These considerations will be useful in the search for other such systems.     

Preparation and Thermoelectric Properties of LaGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> and SmGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript>

Thermoelectric materials are attractive since they can recover waste heat directly in the form of electricity. In this study, the thermoelectric properties of ternary rare-earth sulfides LaGd_1+x S₃ (x = 0.00 to 0.03) and SmGd_1+x S₃ (x = 0.00 to 0.06) were investigated over the temperature range of 300 K to 953 K. These sulfides were prepared by CS₂ sulfurization, and samples were consolidated by pressure-assisted sintering to obtain dense compacts. The sintered compacts of LaGd_1+x S₃ were n-type metal-like conductors with a thermal conductivity of less than 1.7 W K⁻¹ m⁻¹. Their thermoelectric figure of merit ZT was improved by tuning the chemical composition (self-doping). The optimized ZT value of 0.4 was obtained in LaGd_1.02S₃ at 953 K. The sintered compacts of SmGd_1+x S₃ were n-type hopping conductors with a thermal conductivity of less than 0.8 W K⁻¹ m⁻¹. Their ZT value increased significantly with temperature. In SmGd_1+x S₃, the ZT value of 0.3 was attained at 953 K.     

Thermoelectric Properties of <Emphasis Type="Italic">In Situ</Emphasis> Formed Bi<Subscript>0.85</Subscript>Sb<Subscript>0.15</Subscript>/Bi-Rich Particles Composite

A Bi-15 at.%Sb alloy, homogenized by equal channel angular extrusion (ECAE) at T = 523 K, has been treated just above its solidus temperature, causing segregation of a secondary Bi-rich phase at the grain boundaries. This process results in an in situ composite. The thermoelectric properties of the composite have been measured in the range of 5 K < T < 300 K. The results are compared with those of the homogeneous alloy. The presence of a Bi-rich phase improves the Seebeck coefficient at T < 50 K, and enhances the electrical conductivity by a factor of 1.4 at T = 300 K up to a factor of 3.4 at T = 50 K; unfortunately, the thermal conductivity also increases by about 50% in the same temperature range. As a result, the figure of merit, Z, is slightly suppressed above T = 110 K, but increases at lower temperatures, reaching a peak value of 4.2 × 10⁻³ K⁻¹ at T = 90 K. The power factor considerably increases over the whole temperature range, rendering this material suitable as the n-type leg of a cryogenic thermoelectric generator for cold energy recovery in a liquefied natural gas plant.     

Stability of Skutterudite Thermoelectric Materials

By multifilling with La, Ba, Ga, Ti, Yb, Ca, Al, and In, the dimensionless figure of merit ZT of filled skutterudites has been improved in this work. ZT reached 0.75 for p-type (La,Ba,Ga,Ti) _x (Fe,Co)₄Sb₁₂ (x = 0.8 to 1.0) and 1.0 for n-type (Yb,Ca,Al,Ga,In) _y (Co,Fe)₄Sb₁₂ (y = 0.7 to 0.9). After annealing at 873 K for 180 h, 300 h, 710 h, 1000 h, and 5000 h in vacuum, the Seebeck coefficient S and the electrical resistivity ρ of the samples increased while the thermal conductivity λ decreased with increasing annealing time. As a result, the ZT values of both p- and n-type skutterudites remained unchanged or were slightly improved, demonstrating the excellent thermal stability of these skutterudites.     

Effects of SiC Nanodispersion on the Thermoelectric Properties of <Emphasis Type="Italic">p</Emphasis>-Type and <Emphasis Type="Italic">n</Emphasis>-Type Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Based Alloys

Polycrystalline p-type Bi_0.5Sb_1.5Te₃ and n-type Bi₂Te_2.7Se_0.3 thermoelectric (TE) alloys containing a small amount (vol.% ≤5) of SiC nanoparticles were fabricated by mechanical alloying and spark plasma sintering. It was revealed that the effects of SiC addition on TE properties can be different between p-type and n-type Bi₂Te₃-based alloys. SiC addition slightly increased the power factor of the p-type materials by decreasing both the electrical resistivity (ρ) and Seebeck coefficient (α), but decreased the power factor of n-type materials by increasing both ρ and α. Regardless of the conductivity type, the thermal conductivity was reduced by dispersing SiC nanoparticles in the Bi₂Te₃-based alloy matrix. As a result, a small amount (0.1 vol.%) of SiC addition increased the maximum dimensionless figure of merit (ZT _max) of the p-type Bi_0.5Sb_1.5Te₃ alloys from 0.88 for the SiC-free sample to 0.97 at 323 K, though no improvement in TE performance was obtained in the case of n-type Bi₂Te_2.7Se_0.3 alloys. Importantly, the SiC-dispersed alloys showed better mechanical properties, which can improve material machinability and device reliability.     

Design and Modeling of HgCdTe nBn Detectors

An n-type mercury cadmium telluride (HgCdTe) unipolar nBn infrared detector structure is proposed as a means of achieving performance limited by intrinsic thermal carrier generation without requirements for p-type doping. Numerical modeling was utilized to calculate the current–voltage and optical response characteristics and detectivity values for HgCdTe nBn and p–n junction devices with a cut-off wavelength of 12 μm for temperatures between 50 K and 300 K. Calculations demonstrate similar dark current density, responsivity, and detectivity values within 10% for the long-wavelength infrared (LWIR) nBn detector compared with the p–n junction structure for temperatures from 50 K to 95 K. These results show that the HgCdTe nBn device may be a promising alternative for achieving high performance using a simplified device structure while circumventing issues related to p-type doping in current p–n junction technology such as achieving low, controllable doping concentrations, and serving as a basis for next-generation device structures.     

Planar <Emphasis Type="Italic">n</Emphasis>-on-<Emphasis Type="Italic">p</Emphasis> HgCdTe FPAs for LWIR and VLWIR Applications

Mainly driven by space applications, mercury cadmium telluride (MCT) focal-plane arrays (FPAs) have been successfully developed for very long wavelengths (λ _CO > 14 μm at 55 K). For this purpose, the standard n-on-p technology based on MCT grown by liquid-phase epitaxy (LPE) and involving vacancy doping has been modified to extrinsic doping by a monovalent acceptor. Due to the planar diode geometry obtained by ion implantation, most of the carrier generation volume is located in the p-type region with a thickness of approximately 8 μm. According to our understanding, the Shockley–Read centers connected with the Hg vacancies are thus significantly reduced. This situation should lead to longer minority-carrier lifetimes and smaller generation rates under equilibrium conditions, therefore yielding lower dark current. We indeed observe a reduction by a factor of approximately 15 by using extrinsic doping. Recent dark current data obtained in the temperature range from 55 K to 85 K on 288 × 384 FPAs with λ _CO(60 K) = 12 μm, either intrinsically or extrinsically doped, corroborate this finding. These data, new results on a 112 × 112 pixel demonstrator array with λ _CO(55 K) = 14.4 μm, and earlier measurements are compared with Tennant’s Rule 07 established for p-on-n technology.     

Electron Density Distribution in Mn<Subscript>4</Subscript>Si<Subscript>7</Subscript>

Single crystal diffraction measurements were successfully carried out for spherical fine grains grown as single crystals of 0.05–0.2 mm in diameter. Local modulations in the silicon layers were also observed by means of high-resolution electron microscopy. The metallic tin–flux technique was used for crystal growth. The Fourier synthesis and maximum entropy method (MEM) were applied to x-ray diffraction data to obtain electron density distribution maps. Mn₄Si₇ is one of the most promising p-type thermoelectrics useable from 400 K to 700 K. The crystal structure is described in terms of a chimney-ladder structure. The doping effect, by which the system becomes n-type and a structure modulation occurs, was reported by our group previously. The resultant electron density maps were compared with those from the band calculation. The MEM calculation shows the displacement of silicon positions.     

Synthesis and Characterization of New Ceramic Thermoelectrics Implemented in a Thermoelectric Oxide Module

Novel thermoelectric oxides were developed, produced, and characterized to demonstrate their promising thermoelectric conversion potential in a thermoelectric converter. Four-leg thermoelectric oxide modules were fabricated by combining p- and n-type oxide thermoelements made of pressed polycrystalline GdCo_0.95Ni_0.05O₃ and CaMn_0.98Nb_0.02O₃, respectively. In these modules, the p- and n-type thermoelements were connected electrically in series and thermally in parallel. The materials were joined by electrical contacts consisting of a Ag/CuO composite material. Fairly good thermal contacts were ensured by pressing the thermoelements between alumina substrates. Cross-sections of the alumina/Ag–CuO mixture/thermoelement interface were investigated by scanning electron microscopy. The temperature distribution across the module was monitored using K-type thermocouples and a micro-infrared (IR) camera. The open-circuit voltage and the load voltages of the module were measured up to a temperature difference of ΔT = 500 K while keeping the temperature of the cold side at 300 K. The output power and internal resistance were calculated. The characteristics of the module evaluated from electrical measurements were compared with respective values of the p- and n-type leg materials. An output power of 0.04 W at ΔT = 500 K led to a power density of ~0.125 W/cm³, where the volume of thermoelectric material was determined by a cross-section of 4 mm × 4 mm and a leg length of 5 mm.     

First-Principles and Experimental Studies of Y-Doped Mg<Subscript>2</Subscript>Si Prepared Using Field-Activated Pressure-Assisted Synthesis

The thermoelectric properties of Y-doped (1000 ppm, 2000 ppm, 3000 ppm) Mg₂Si fabricated using field-activated pressure-assisted synthesis (FAPAS) have been characterized using measurements of electrical resistivity (ρ), Seebeck coefficient (S), and thermal conductivity (κ) at temperatures ranging from 285 K to 810 K. The Y-doped Mg₂Si samples were n-type in the measured temperature range. A first-principles calculation revealed that the Y atoms were expected to be primarily located at Mg sites. In sample doped with 2000 ppm Y, which exhibited the best electrical and thermal conductivity, the absolute value of the Seebeck coefficient increased in the temperature range of 320 K to 680 K, being higher than that of undoped Mg₂Si. Moreover, this sample exhibited a higher level of electrical conductivity and a higher power factor. In addition, introduction of Y decreased the thermal conductivity appreciably, indicating that Y dopants are favorable for improving the properties of Mg₂Si.     

Thermoelectric Properties of <Emphasis Type="Italic">p</Emphasis>-Type Mg<Subscript>2.00</Subscript>Si<Subscript>0.25</Subscript>Sn<Subscript>0.75</Subscript> with Li and Ag Double Doping

Mg₂Si_1−x Sn _x -system solid solutions are ecofriendly semiconductors that are promising materials for thermoelectric generators in the middle temperature range. To produce a thermoelectric device, high-performance p- and n-type materials must be balanced. In this paper, p-type Mg_2.00Si_0.25Sn_0.75 with Li and Ag double doping was prepared by the liquid–solid reaction method and hot-pressing. Effects of Li and Ag double doping on thermoelectric properties were investigated in the temperature range from room temperature to 850 K. All sintered compacts were identified as single-phase solid solutions with anti-fluorite structure. The carrier concentration increased with the double doping. The temperature dependence of resistivity of the double-doped samples was similar to that of a metal. The seebeck coefficient increased with temperature to a maximum value and then decreased in the intrinsic region. Thermal conductivity decreased linearly with increasing temperature, reaching a minimum near the intrinsic region, and then increased rapidly because of the contribution of the bipolar component. The dimensionless figure of merit reached 0.32 at 610 K for Mg_2.00Si_0.25Sn_0.75 double-doped with Li-5000 ppm and Ag-20000 ppm.